Catalytic conversion of hydrocarbons



1944- J. D. DANFORTH 2,356,978 CATALYTIC CONVERSION OF HYDROCARBONS Filed June 27, 1942 a0- so :EerceniB o 1: weighc in ZrO B 0 Composiieg drocarbon fractions Patented Aug. 29, 1944 os'raarric oouvansron F nrpnocaaaous Application June 27, 1942, Serial No. 448,761 ('01. 196-52) 7 9Claims.

This is a continuation-in-part of my co-pending application Serial No. 18, 1939.

The present invention relates to a process for the lysts to produce substantial yields of lower boilin: fractions vwithin the gasoline boiling range anti-knock value. The process is applicable to conversions involving single hydrocarbons, synthetically produced and shales. bons may be processed, more frequently the hycharged to 'the'process are 01' a distillatercharacter and vaporizable without substantial decomposition.

304,697, iiled November presence of cata- In general the invention is concerned with the modification of hydrocarbon conversion processes involving the use of specific catalysts which se-' leetively promote the hydrocarbon reactions involved in the formation 01- high anti-knock sasoline.

It is recoimized that drocarbon fractions are cracked in the presence commercial processes are in operation in which relatively high boiling hyor boric oxide, indicating that the precise efl'ect of. the addition or able. For example, the catalytic activity oi alusimilarly, the addition oi. boricoxide to silica does not produce an substantial improvement in the catalytic activity 01' the silica.

In one specific embodiment the present invention comprises subjecting hydrocarbon oil at elevated temperatures and relatively low superhydrated zirconia to produce substantial yields of lush anti-knock gasoline.

The catalyst which of the present invention consists of unknown portlonsof boric oxide, the composite exhibiting a high order of activity i'or accelerating cracking reactions. The catalyst composites maybe prepared by a number 01' alternative methods which a heretofore tutes the active catalyst. The components of the combination of the the active catalyst.

The character and will depend more percent zirconia. iavorable found within the range of .45 to of boric oxide. Catalytic efiects of activity was moi percent lower order have been experienced outside of these ranges using the essential components, and different ranges 01' activity may be expected when using this substance is not predictcharacterizes the processcomposite of zirconia with minor pro- 7 some oxide and to 55 mol" different methods of compositing. For example, when zirconia is impregnated with boric oxide, catalysts of high activity may be prepared with a boric oxide content of only 8%. In general, however, minor proportions of boric oxide are used with major proportions of the zirconia.

Numerous methods of compositing the boric oxide with the zirconia are possible and the scope of the present invention is not considered as limited to the methods here described. A suitable grade of zirconia, for example a dried gel of this oxide may be mixed in powdered condition with boric oxide and the composite may be heated at an ordinary drying temperature, for example about 200 C. Upon cooling, the powdered mixture may be consolidated and formed into particles by conventional processes such as pressing, pelleting and extruding. In an alternative procedure salts such as zirconium oxychloride, etc., which decompose on heating in the presence of moisture to zirconium oxide may be intimately admixed with the boric oxide and the mixture heated until the salt has decomposed and formed an oxide. The oxychloride need not necessarily be used, other salts such as, for example, the nitrate, sulfate, acetate, and oxalate of zirconium being utilizable. As an example of further alternative methods, boric anhydride as well as boric acid, or a perborate, may be dissolved in water and'a soluble salt of zirconium added in the desired proportions. Alkaline precipitants such as ammonium'hydroxideffor example, may then be added to precipitate zirconia hydrate which absorbs the boron compound, whereupon the precipitate is filtered and dried, washed if necessary and formed into particles as above.

More or less inert materials may be admixed with the zirconia-boric oxide composites to serve as spacing agents and for the purposes of lending support to the catalytic material. These may be present in proportions up to 80%, more or less, of the final catalyst material. Many such materials are generally known such as clay, fuller's earth, bentonite, montmorlllonite, infusorial earth, diatomaceous earth or kieselguhr and zeolites, glauconites, etc., also dried silica gel, pumice, rutile, ilmenite, chromite, etc.

The catalysts of the present invention may be conveniently used in carrying out reactions when employed as filling material in tubes or chambers in the form of small pellets or granules. The average particle size may vary within the approximate range of 2 to- 10 mesh, more or less, and may apply either to pellets of uniform size, in short cylindrical shapes, or to particles of irregular shape produced as, for example, by consolidating and sizing powdered catalytic material.

While the simple method of preheating a given fraction of hydrocarbon oil to be processed to a temperature suitable for its conversion in contact with the catalyst, and then passing the vapors over a stationary mass of the catalyst particles, may be employed, it is generally preferable to pass the preheated vapors through the catalyst where the passage of vapors is restricted to definite paths rather than allowing the vapors to have unrestricted contact with large beds of catalytic material. It is thus possible to control more accurately the temperature of the contact materials both in use and during regeneration.

After the passage of oil vapors over the catalyst,

theproducts may beseparated into fractions unsuitable for further cracking, intermediate in- 1 in separate passes so. as to obtain ultimately the maximum utilization of the charging stock in producing the gasoline product. Although the above is more conventional practice, it is also possible to suspend the catalyst in the stream of oil as a powder and treat the suspension under conditions of temperature, pressure and contact time adequate to effect a desired degree of conversion. The normally gaseous fraction separated fro the gasoline product when using the present types of catalysts in cracking contains much larger proportions of readily polymerizable olefins,

more particularly propene and butenes, than are usually present in the gases from ordinary thermal cracking, or cracking with certain other types of catalysts and these olefins may be readily polymerized using thermal and/or catalytic processes to produce additional yields of gasoline to be blended, if desired, with the primary gasoline product'produced in the process. The application of the present invention to conversion of hydrocarbon fractions besides being characterized by the use of novel catalysts is also characterized by the moderate operating conditions of temperature and pressure. tures employed in contact with the catalysts may be within the range of about 750 F. and about 1100 F., and substantially atmospheric pressure or moderately superatmospheric pressure up to several hundred pounds per square inch may be used. The pressures are somewhat governed by the fiow conditions through the-vaporizing and conversion zones and the subsequent separating, fractionating and collecting equipment but are most frequently. below 100 pounds per square inch.

The following specific examples are given to illustrate the process of the invention, and the methods of catalyst preparation therefor. The process should not be considered as limited to these examples of the process or to the particular methods of catalyst preparation.

Example I In this example a catalyst was prepared containing approximately 40 mol percent of boric anhydride and 60 mol percent of zirconia. 462 parts by weight of hydrated zirconia and 35 parts by weight of boric oxide were mixed and dried at approximately 220-240 F. The dried material was pulverized and then consolidated to form granules of approximately 6-10 mesh particle size. The granules were then heated at approximately 900 F. for one hour. Particles oi this catalyst were used as filler in a reactor and a parafiinic gas oil was contacted with the catalyst at a temperature of 932 F., a superatmospheric pressure of 15 pounds per square inch, using an hourly liquid space velocity of 4. A 33% yield of 400 F. gasoline was obtained during the first hour and at the end of the sixth hour the gasoline production had dropped to 23%, the total gasoline having an octane number. of approximately 79. After catalyst regeneration a total yield for a six hour process period of 26.5%

Temperaliquid hourly space velocity of 1, 22.7% of gasoline was obtained having an octane number of approximately 78.

Tests were conducted to show the activities of zirconia alone and boric oxide alone. The

zirconia was made by following the 'same procedure as in the preparation of the zirconiaboric oxide without the addition of the boric oxide, and boric oxide of 6 to mesh size granules was prepared by grinding and sizing a fused and cooled cake. Tests were then conducted with these two materials by passing a parafiinic gas oil over them at 932 F., pounds superatmospheric pressure and an hourly liquid space velocity of 4, and it was found that pure zirconia gave a yield of gasoline of 7% by volume of the charge while the boric oxide gave a yield of 2%. These tests compared with the preceding tests on the zirconia-boric oxide mixture indicate that the effects of the two components in the composite catalysts are more than additive.

Example II A series of catalysts varying in composition from one consisting entirely of zirconia to one consisting entirely of boric oxide were prepared by heating zirconium oxychloride hydrate alone and in admixture with increasing amounts of boric oxide. A series of eight catalysts were prepared and tested by a standard method involving passage of a Pennsylvania gas oil over the catalysts at a temperature of 932 F., substantially atmospheric pressure and an hourly space velocity of 8 for a period of two hours. The significant results obtained in these tests, indicating the variations in catalyst activity with composition are shown in the attached graph which was made by plotting the composition of the catalysts against the volume percent gasoline produced based on the gas oil charged.

Reference to the graph shows that the activity of the catalysts measured by the percentage of gasoline produced under the standard test conditions passed through a maximum at about 27% boric oxide by weight in the zirconia boric oxide composites. After about 50% boric oxide is exceeded the activity continues at a slowly decreasing rate until an activity correspondinggasoline production is reached corto about 2% responding to pure boric oxide. On the other end of the scale the pure zirconium oxide shows a yield of about 6 /2% of gasoline. Practical yields of gasoline were obtained with composites containing from about 10 to about percent of boric oxide.

1 claim as my invention:

1. A process for the conversion of hydrocarbons, which comprises subjecting said hydrocarbons at a cracking temperature to contact with a catalyst comprising essentially zirconium oxide and boron oxide.

2. A process for the conversion of hydrocarbons which comprises subjecting a hydrocarbon oil at a temperature of from about 750 F. to about 1100 F. to contact with a catalyst com prising essentially zirconium oxide and boron oxide.

3. A process for converting a hydrocarbon oil to substantial yields of high anti-knock motor fuel which comprises subjecting said oil at a temperature of from about 750 F. to about 1100 F. to contact with a calcined mixture of zirconium oxide and boric oxide.

4. A hydrocarbon conversion catalyst comprising essentially a calcined mixture of zirconium oxide and boric oxide.

5. A hydrocarbon conversion catalyst comprising essentially a calcined mixture of zirconium oxide, boric oxide and a material.

6. A process for the conversion of hydrocarbons which comprises subjecting said hydrocarbons at a cracking temperature to contact with a composite catalyst comprising essentially zirconium oxide and boric oxide, the weight percentage of boric oxide in the composite being in the range from about 10 to about 45%.

7. A process for the conversion of hydrocarbons which comprises subjecting said hydrocarbons at a temperature of from about 750 F. to 1100 F. to contact with a composite catalyst comprising essentially zirconium oxide and boric oxide, the weight percentage of boric oxide in the composite being in the range from about 10 to about 45%.

8. A hydrocarbon conversion catalyst comprising essentially a calcined mixture of zirconium oxide and-boric oxide in which the weight percentage of boric oxide ranges from about 10 to about 45%.

9. A hydrocarbon conversion catalyst composite comprising essentially a calcined mixture of zirconium oxide, boric oxide and a relatively inert spacing material, the percentage by weight of the zirconium oxide content being relatively greater than that of the boric oxide.

JOSEPH D. DANFOR'I'H.

relatively inert spacing 

